Mechanistic aspects of the dehydration and dehydrohalogenation of halo-hydroxyformaldoxime conformers. A quantum chemical model study
Φόρτωση...
Ημερομηνία
Συγγραφείς
Tsipis, A. C.
Tsipis, C. A.
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
Wiley
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
Journal of Computational Chemistry
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
A detailed exploration of the configurational and conformational space of chloro- and bromo-hydroxyformaldoximes, Xhfaox (X = Cl, Br) has been carried out with the aid of the B3LYP level of density functional theory, using the 6-31G(d,p) basis set. The most stable configuration in each series of the Clhfaox and Brhfaox conformers corresponds to the Z-s-cis, s-trans configuration, while the highest energy Z-(s-trans, s-cis) conformers were found at 7.0(7.6) and 6.0(6.6) kcal mol�1, respectively, at the B3LYP(QCISD(T)) levels of theory. Saddle points were also located on the PES of the Clhfaox and Brhfaox compounds corresponding to Z-(s-cis, s-cis) conformers at 13.8(14.9) and 13.6(14.6) kcal mol�1, respectively, at the B3LYP(QCISD(T)) levels. Upon dehydration Xhfaox could afford a number of isomeric CXNO species. The dehydration processes of Xhfaox are predicted to be endothermic, the computed heats of reactions found in the range of 20.5 to 86.2 kcal mol�1 and 15.9 to 100.4 kcal mol�1 at the B3LYP and QCISD(T) levels, respectively. The reaction pathways for the addition of water to halo-fulminates yielding the most stable Xhfaox conformers was predicted to be concerted with a single transition structure, but are asynchronous with activation barriers of 32.8 and 43.0 kcal mol�1 for the chloro- and bromo-derivatives, respectively. The PES governing the isomerization reactions of the CXNO isomers have also been calculated, and possible isomerization pathways have been delineated. Upon dehydrohalogenation the Xhfaox conformers yield hydroxy-isocyanate or hydroxy-fulminate, the former being more stable by 31.8(18.8) kcal mol�1 at the B3LYP(QCISD(T)) levels of theory. The reaction pathways for the addition of HX to hydroxy-isocyanate were predicted to be slightly exothermic, the heats of reactions being �3.2 and �5.5 kcal mol�1, respectively, and have to surmount high activation barriers of 39.7 and 35.0 kcal mol�1, respectively. Similarly, the addition of HX to hydroxy-fulminate was predicted to be much more exothermic, the heats of reactions being �34.7 and �37.3 kcal mol�1, respectively, and have to surmount much lower activation barriers of only 10.5 and 7.5 kcal mol�1 respectively, at the B3LYP level. Finally, calculated structures, relative stability, and bonding properties of all stationary points located on the PES of the systems and reactions studied are thoroughly discussed with respect to computed electronic properties.
Περιγραφή
Λέξεις-κλειδιά
halo-hydroxyformaldoxime conformers, dehydration reaction profile, dehydrohalogenation reaction profile, isomerization processes, quantum chemical study
Θεματική κατηγορία
Παραπομπή
Σύνδεσμος
http://onlinelibrary.wiley.com/doi/10.1002/jcc.10116/abstract;jsessionid=7EDF75657A9675CF92734E579DE50918.f03t01
Γλώσσα
en
Εκδίδον τμήμα/τομέας
Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας